JP2017128563A - Carbazole compound and use therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a carbazole compound that has a high capability of inhibiting electrons and contributes to the higher efficiency and longer life of an organic EL element.SOLUTION: A carbazole compound has phenothiazine-5-ium represented by formula (1) (X is a 1,4-phenylene group or 1,3-phenylene group; Y is S or O; R-Rindependently represent H, a methyl group or NA rAr, provided that at least one of R-Ris NA rAr; Arand Arindependently represent a C6-18 aromatic hydrocarbon group or a 4-(carbazole-9-yl) phenyl group, each of which is optionally substituted with a methyl group or a methoxy group).SELECTED DRAWING: None

Description

  The present invention relates to a carbazole compound having a phenothiazine ring or a phenoxazine ring and an organic EL device using the same.

  Organic EL devices featuring self-light emission can be thinned because they do not require a backlight used in liquid crystal panels, and have the advantage of flexible performance that can make the screen curved. In recent years, research has been actively conducted as a display and lighting, and it has already been put into practical use for a mobile phone display, a television, and the like.

  In general, an organic EL element has a structure in which a hole transport material, a light emitting material, and an electron transport material are laminated between an anode and a cathode. However, in order to achieve low power consumption and long life at present. A multilayer laminated structure in which a hole injection material, an electron injection material, a hole blocking material, and the like are inserted has become the mainstream. As the hole transport material, an amine compound having an appropriate ionization potential and hole transport ability is used. For example, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter, NPD is abbreviated as NPD), but it is difficult to say that the driving voltage, luminous efficiency, and durability of an element using NPD for the hole transport layer are sufficient. Furthermore, in recent years, organic EL elements using a phosphorescent material for a light emitting layer have been developed, and a hole transport material having a high triplet level is required for an element using phosphorescent light emission. NPD is not sufficient from the point of triplet level, and for example, it has been reported that the organic EL element in which a phosphorescent material having green light emission and NPD are combined reduces the luminous efficiency (for example, non-patent Reference 1).

  Against this background, carbazole compounds have recently been reported (see, for example, Patent Documents 1 and 2). However, since the aromatic condensed ring of pyrene ring and anthracene ring described in Patent Documents 1 and 2 has a low triplet level and has an electron accepting property, a device using a green phosphorescent material has high luminous efficiency. Difficult to get. Therefore, for an organic EL element, it is desired to develop a hole transport material that can further reduce the driving voltage, increase the light emission efficiency, and extend the lifetime.

JP 2008-078362 A JP 2008-195841 A

Journal of Applied Physics, 2004, 95, 7798.

  An object of the present invention is to provide a specific carbazole compound that has an electron blocking function as compared with a conventionally known carbazole compound and contributes to high emission efficiency and long life of an organic EL device.

  As a result of intensive studies, the present inventors have found a carbazole compound represented by the following general formula (1) having a phenothiazine ring or a phenoxazine ring via a phenylene group at the 9-position of the carbazole ring, thereby completing the present invention. It came to.

(In the formula, X represents a 1,4-phenylene group or a 1,3-phenylene group. Y represents a sulfur or oxygen atom. R ^{1 to} R ⁸ each independently represents a hydrogen atom, a methyl group, or A group represented by the following general formula (2) is represented, and at least one of R ^{1 to} R ⁸ is a group represented by the following general formula (2).

(In the formula, Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 18 carbon atoms or a 4- (carbazol-9-yl) phenyl group, and these groups are each independently And may have a methyl group or a methoxy group.)

  Since the carbazole compound of the present invention has an electron donating phenothiazine ring or phenoxazine ring at a specific position as shown in the general formula (1), the electron blocking ability is higher than that of conventionally known carbazole compounds. In addition, the decomposition of the material on the hole transport side due to the inflow of electrons can be suppressed, and the hole transport property and the excited triplet state are excellent. For this reason, the organic EL element using the carbazole compound of the present invention is excellent in luminous efficiency and lifetime as compared with a conventionally known organic EL element using a carbazole compound.

  Hereinafter, the present invention will be described in detail.

  In the carbazole compound represented by the general formula (1), X represents a 1,4-phenylene group or a 1,3-phenylene group. Among these, a 1,4-phenylene group is preferable from the viewpoint of the luminous efficiency of the organic EL element.

  In the carbazole compound represented by the general formula (1), Y represents a sulfur or oxygen atom. Among these, an oxygen atom is preferable in terms of excellent stability of the compound.

In the carbazole compound represented by the general formula ^(1), R 1 ~R ⁸ each independently represent a hydrogen atom, a group represented by a methyl group, or the general formula (2), R ¹ ~ At least one of R ⁸ is a group represented by the general formula (2). In terms of hole transport characteristics and availability of raw materials, R ¹ , R ³ , R ⁶ and R ⁸ are each independently a hydrogen atom or a methyl group, and R ² , R ⁴ , R ⁵ And R ⁷ each independently represents a hydrogen atom, a methyl group or a group represented by the general formula (2), and at least one of R ² , R ⁴ , R ⁵ and R ⁷ is represented by the general formula (2 R ¹ and R ⁸ are each a hydrogen atom, R ³ and R ⁶ are each independently a hydrogen atom or a methyl group, and R ² , R ⁴ , R ⁵ and R ⁷ each independently represent a hydrogen atom, a methyl group, or a group represented by the general formula (2), and at least one of R ² , R ⁴ , R ⁵ and R ⁷ is represented by the general formula ( more preferably a group represented by ^{2), R 1, R 3} , R 6 and ^{R 8} are hydrogen atoms, R , ^R 4, ^{R 5} and ^{R 7} are each independently a hydrogen atom, a group represented by a methyl group, or general formula ^(2), at least one of R ^2, R 4, ^{R 5} and ^{R 7} More preferably, ^one is a group represented by the general formula (2), R ¹ , R ³ , R ⁶ and R ⁸ are hydrogen atoms, and R ² , R ⁴ , R ⁵ and R ⁷ are each Independently, it represents a hydrogen atom or a group represented by the general formula (2), and at least one of R ² , R ⁴ , R ⁵ and R ⁷ is a group represented by the general formula (2). More preferred.

In the carbazole compound represented by the general formula (1), Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 18 carbon atoms or a 4- (carbazol-9-yl) phenyl group. And these groups may each independently have a methyl group or a methoxy group.

The aromatic hydrocarbon group having 6 to 18 carbon atoms in Ar ¹ and Ar ^2, is not particularly limited, for example, a phenyl group, biphenylyl group, terphenylyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, a triphenylenyl group Or a benzofluorenyl group (these groups may each independently have a methyl group or a methoxy group, and the number thereof is not particularly limited).

Specific examples of Ar ¹ and Ar ² include phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3, 4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl Group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 2-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 2-methoxy-4-methylphenyl group, 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl Group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-biphenylyl group 3-biphenylyl group, 2-biphenylyl group, 2-methyl-1,1′-biphenyl-4-yl group, 3-methyl-1,1′-biphenyl-4-yl group, 2′-methyl-1, 1'-biphenyl-4-yl group, 3'-methyl-1,1'-biphenyl-4-yl group, 4'-methyl-1,1'-biphenyl-4-yl group, 2,6-dimethyl- 1,1′-biphenyl-4-yl group, 2,2′-dimethyl-1,1′-biphenyl-4-yl group, 2,3′-dimethyl-1,1′-biphenyl-4-yl group, 2,4′-dimethyl-1,1′-biphenyl-4-yl group, 3,2′-dimethyl group Ru-1,1′-biphenyl-4-yl group, 2 ′, 3′-dimethyl-1,1′-biphenyl-4-yl group, 2 ′, 4′-dimethyl-1,1′-biphenyl-4 -Yl group, 2 ', 5'-dimethyl-1,1'-biphenyl-4-yl group, 2', 6'-dimethyl-1,1'-biphenyl-4-yl group, p-terphenyl group, m-terphenyl group, o-terphenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylnaphthalen-1-yl group, 4-methylnaphthalen-1-yl group, 6-methylnaphthalen-2-yl Group, 4- (1-naphthyl) phenyl-1-yl group, 4- (2-naphthyl) -1-yl group, 2-anthryl group, 9-anthryl group, 2-fluorenyl group, 9,9-dimethyl- 9H-fluoren-2-yl group, 9-phenanthryl group, 2-phenanthryl group, 2 Triphenylenyl group, benzofluorenyl group, fluoranthenyl group, a pyrenyl group, or 4- (carbazol-9-yl) can be exemplified a phenyl group, but is not limited thereto.

In terms of hole transport properties, Ar ¹ and Ar ² in the carbazole compound represented by the general formula (1) of the present invention are each independently a phenyl group, a biphenylyl group, a terphenyl group, a fluorenyl group, or It is preferably a 4- (carbazol-9-yl) phenyl group (for these series of groups, which may have a methyl group or a methoxy group), a phenyl group, a tolyl group, a 4-biphenylyl group, p -Terphenyl-4-yl group, 9,9-dimethyl-9H-fluoren-2-yl group, and 4- (carbazol-9-yl) phenyl group are more preferable.

  Further, from the viewpoint of excellent hole transportability and triplet level, in the general formula (1), the substitution position of the amino group with respect to the carbazole ring is 2, 3, 4, 5, 6 or 7 It is preferable that it is a 2nd, 4th, 5th, or 7th position. Examples of the compound include carbazole compounds represented by the following general formula (3) or (4).

(In the formula, Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 18 carbon atoms or a 4- (carbazol-9-yl) phenyl group, and these groups are each independently R ^{1 to} R ⁷ each independently represents a hydrogen atom or a methyl group, and X represents a 1,4-phenylene group or a 1,3-phenylene group. Y represents a sulfur or oxygen atom.)
The definitions and preferred ranges of Ar ¹ , Ar ² , R ^{1 to} R ⁷ , X and Y shown in the general formulas (3) and (4) are the same as those described in the general formula (1). It is.

  Hereinafter, preferred compounds of the carbazole compound represented by the general formula (1) are exemplified, but the present invention is not limited to these compounds.

  Among these exemplified compounds, A6, A7, A11, A14, A18, A26, A31, A38, A86, A87 are preferable because they are excellent in triplet level, hole transport ability, ease of synthesis and electron blocking function. A91, A107, B6, B7, B10, B11, B12, B14, B18, B26, B31, B38, B81, B86, B87, B91, B98, or B106 are preferred.

  The carbazole compound represented by the general formula (1) is a known method (Tetrahedron Letters, 1998, using a 9H-carbazole compound in which at least one of 1-position to 8-position of the carbazole ring is halogenated as a raw material. 39, 2367). For example, in the case of a 9H-carbazole compound in which the 2-position of the carbazole ring is halogenated, it can be synthesized by the following route.

  A 9H-carbazole compound halogenated at the 2-position represented by the general formula (5) and an aryl compound having a halogen atom represented by the general formula (6), in the presence of a base, a copper catalyst or a palladium catalyst To give a 2-halogenated-9-substituted carbazole compound represented by the general formula (7). Further, the obtained 2-halogenated-9-substituted carbazole compound represented by the general formula (7) and the secondary amine compound represented by the general formula (8) are reacted with a copper catalyst or The reaction is carried out using a palladium catalyst.

[Wherein, X, Y, Ar ¹ and Ar ² , R ^{1 to} R ⁸ represent the same definition as in the general formula (1). A and B each independently represent a halogen atom (iodine, bromine, chlorine, or fluorine). ]
The compounds represented by the general formulas (5), (6) and (8) can be synthesized based on generally known methods, or commercially available compounds can also be used.

  The carbazole compound represented by the general formula (1) of the present invention can be used as a light emitting layer, a hole transport layer or a hole injection layer of an organic EL device. In addition, it is preferable that the carbazole compound represented by the general formula (1) has high purity in terms of hole transport characteristics and device lifetime.

  For the light emitting layer when the carbazole compound represented by the general formula (1) is used as a hole injection layer or a hole transport layer of an organic EL device, a conventionally known fluorescent or phosphorescent light emitting material is used. Can be used. The light emitting layer may be formed of only one kind of light emitting material, or one or more kinds of light emitting materials may be doped in the host material.

  When forming the hole injection layer and / or hole transport layer made of the carbazole compound represented by the general formula (1), two or more kinds of materials may be contained or laminated as necessary. For example, oxides such as molybdenum oxide, 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, hexacyanohexahexa A known electron-accepting material such as azatriphenylene may be contained or laminated.

  Moreover, the carbazole compound represented by the general formula (1) of the present invention can also be used as a light emitting layer of an organic EL device. When the carbazole compound represented by the general formula (1) is used as the light emitting layer of the organic EL device, the carbazole compound is used alone, doped into a known light emitting host material, or a known light emitting dopant is used. Can be used by doping.

  As a method for forming a hole injection layer, a hole transport layer, or a light emitting layer containing the carbazole compound represented by the general formula (1), for example, a known method such as a vacuum deposition method, a spin coating method, or a casting method is used. The method can be applied.

  As a basic structure of the organic EL device that can obtain the effects of the present invention, those including a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are preferable. Layers may be omitted, or vice versa.

  The anode and cathode of the organic EL element are connected to a power source through an electrical conductor. By applying a potential between the anode and the cathode, the organic EL element operates and emits light.

  Holes are injected into the organic EL element from the anode, and electrons are injected into the organic EL element at the cathode.

  The organic EL element is typically placed on a substrate, and the anode or cathode can be in contact with the substrate. The electrode in contact with the substrate is called the lower electrode for convenience. Generally, the lower electrode is an anode, but the organic EL element of the present invention is not limited to such a form.

  The substrate may be light transmissive or opaque depending on the intended emission direction. The light transmission characteristics can be confirmed by electroluminescence emission through the substrate. Generally, transparent glass or plastic is used as the substrate in such a case. The substrate may be a composite structure including multiple material layers.

  When the electroluminescent emission is confirmed through the anode, the anode is formed by passing or substantially passing through the emission.

  The general transparent anode (anode) material used in the present invention is not particularly limited, and examples thereof include indium-tin oxide (ITO), indium-zinc oxide (IZO), and tin oxide. . Other metal oxides such as aluminum or indium doped tin oxide, magnesium-indium oxide, or nickel-tungsten oxide can also be used. In addition to these oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, or metal sulfides such as zinc sulfide can be used as the anode.

  The anode can be modified with plasma deposited fluorocarbon. If electroluminescence emission is confirmed only through the cathode, the transmission properties of the anode are not critical and any conductive material that is transparent, opaque or reflective can be used. Examples of conductors for this application include gold, iridium, molybdenum, palladium, platinum and the like.

  A plurality of hole transporting layers such as a hole injection layer and a hole transport layer can be provided between the anode and the light emitting layer. The hole injection layer and the hole transport layer have a function of transmitting holes injected from the anode to the light emitting layer. By interposing these layers between the anode and the light emitting layer, the hole injection layer and the hole transport layer are often used in a lower electric field. Holes can be injected into the light emitting layer.

  In the organic EL device of the present invention, the hole transport layer and / or the hole injection layer contains a carbazole compound represented by the general formula (1).

  For the hole transport layer and / or hole injection layer, any one of well-known hole transport materials and / or hole injection materials is selected together with the carbazole compound represented by the general formula (1). Can be used in combination.

  Known hole injection materials and hole transport materials include, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, Examples thereof include oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers. As the hole injecting material and the hole transporting material, those described above can be used, and porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds, particularly aromatic tertiary amine compounds can be used. preferable.

  Representative examples of the aromatic tertiary amine compound and styrylamine compound include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl, N, N′-diphenyl-N, N ′. -Bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (TPD), 2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1- Bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl, 1,1-bis (4-di-p- Tolylaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N′-diphenyl-N, N -Di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) quadri Phenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 ′-[4- (di-p-tolylamino) styryl] stilbene, 4-N, N-diphenyl Amino- (2-diphenylvinyl) benzene, 3-methoxy-4′-N, N-diphenylaminostilbenzene, N-phenylcarbazole, 4,4′-bis [N- (1-naphthyl) -N-phenylamino ] Biphenyl (NPD), 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) and the like. That.

  In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material. The hole injection layer and the hole transport layer may have a single layer structure composed of one or more of the above materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

  The light emitting layer of the organic EL element contains a phosphorescent material or a fluorescent material, and emits light as a result of recombination of electron / hole pairs in this region.

  The emissive layer may consist of a single material that includes both small molecules and polymers, but more commonly consists of a host material doped with a guest compound, where the emission occurs primarily from the dopant, Can have a color.

  Examples of the host material for the light emitting layer include compounds having a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, or an anthranyl group. For example, DPVBi (4,4′-bis (2,2-diphenylvinyl) -1,1′-biphenyl), BCzVBi (4,4′-bis (9-ethyl-3-carbazovinylene) 1,1′-biphenyl ), TBADN (2-tert-butyl-9,10-di (2-naphthyl) anthracene), ADN (9,10-di (2-naphthyl) anthracene), CBP (4,4′-bis (carbazole-9) -Yl) biphenyl), CDBP (4,4′-bis (carbazol-9-yl) -2,2′-dimethylbiphenyl), 9,10-bis (biphenyl) anthracene and the like.

  The host material in the light emitting layer may be an electron transport material as defined below, a hole transport material as defined above, another material that supports hole / electron recombination (support), or a combination of these materials. Good.

  Examples of fluorescent dopants include anthracene, pyrene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compounds, thiopyran compounds, polymethine compounds, pyrylium or thiapyrylium compounds, fluorene derivatives, perifanthene derivatives, indenoperylene. Derivatives, bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, carbostyryl compounds and the like can be mentioned.

  As an example of the phosphorescent dopant, an organometallic complex of a transition metal such as iridium, platinum, palladium, or osmium can be given.

Examples of dopants include Alq ₃ (tris (8-hydroxyquinoline) aluminum)), DPAVBi (4,4′-bis [4- (di-p-tolylamino) styryl] biphenyl), perylene, Ir (PPy) ₃ ( Examples include tris (2-phenylpyridine) iridium (III), FlrPic (bis (3,5-difluoro-2- (2-pyridyl) phenyl- (2-carboxypyridyl) iridium (III)), and the like.

  Examples of the electron transporting material include alkali metal complexes, alkaline earth metal complexes, and earth metal complexes. Examples of the alkali metal complex, alkaline earth metal complex, or earth metal complex include 8-hydroxyquinolinate lithium (Liq), bis (8-hydroxyquinolinato) zinc, and bis (8-hydroxyquinolinate). Copper, bis (8-hydroxyquinolinato) manganese, tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, Bis (10-hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolate) gallium, bis (2-methyl-8-quinolinate) 1-naphthyl Trat aluminum, bis (2-methyl-8-quinolinato) -2-naphthoquinone Trad gallium, and the like.

  A hole blocking layer may be provided between the light emitting layer and the electron transport layer for the purpose of improving carrier balance. Desirable compounds for the hole element layer are BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis (2 -Methyl-8-quinolinolato) -4- (phenylphenolato) aluminum) or bis (10-hydroxybenzo [h] quinolinato) beryllium).

  In the organic EL device of the present invention, an electron injection layer may be provided for the purpose of improving electron injection properties and improving device characteristics (for example, light emission efficiency, constant voltage driving, or high durability).

Preferred compounds for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, etc. Is mentioned. In addition, the above-described metal complexes, alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, SiO ₂ , AlO, SiN, SiON, AlON, Various oxides such as GeO, LiO, LiON, TiO, TiON, TaO, TaON, TaN, and C, and inorganic compounds such as nitride and oxynitride can also be used.

If light emission is confirmed only through the anode, the cathode used in the present invention can be formed from any conductive material. Desirable cathode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, indium , Lithium / aluminum mixtures, rare earth metals and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples at all.

  The analytical instruments and measurement methods used in this example are listed below.

[Material purity measurement (HPLC analysis)]
Measuring device: Tosoh Multi Station LC-8020
Measurement conditions: Column Inertsil ODS-3V (4.6 mmΦ × 250 mm)
Detector UV detection (wavelength 254nm)
Eluent Methanol / Tetrahydrofuran = 9/1 (v / v ratio)
[NMR measurement]
Measuring device: Gemini200 manufactured by Varian
[Mass spectrometry]
Mass spectrometer: Hitachi M-80B
Measuring method: FD-MS analysis [Reduction characteristics]
Measuring device: HA-501 and HB-104 manufactured by Hokuto Denko
Measurement method: Cyclic voltammetry evaluation [Emission characteristics of organic EL elements]
Measuring device: LUMINANCEMETER (BM-9) manufactured by TOPCON
Synthesis Example 1 Synthesis of 2-chloro-9- [4- (10H-phenothiazin-10-yl) phenyl] carbazole

  In a 200 mL three-necked flask under nitrogen flow, 5.0 g (24.8 mmol) of 2-chloro-9H-carbazole, 9.7 g (27.3 mmol) of 10- (4-bromophenyl) -10H-phenothiazine, triphosphate 3 7.9 g (37.2 mmol) of potassium and 40 mL of o-xylene were added, and 56 mg (0.25 mmol) of palladium acetate and 176 mg (0.87 mmol) of tri-tert-butylphosphine were added to the resulting slurry reaction solution. The mixture was added and stirred at 140 ° C. for 5 hours. After cooling to room temperature, 25 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with a saturated aqueous sodium chloride solution, further dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. By recrystallizing the residue (toluene / hexane), 9.2 g (19.4 mmol) of white powder of 2-chloro-9- [4- (10H-phenothiazin-10-yl) phenyl] carbazole was isolated ( Yield 78%, HPLC purity 99.3%).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.13 (d, 1H), 8.05 (d, 1H), 7.70 (d, 2H), 7.58 (d, 2H), 7.46 (s) 3H), 7.35-7.24 (m, 2H), 7.13 (d, 2H), 7.02-6.92 (m, 4H), 6.53 (d, 2H)
¹³ C-NMR (CDCl ₃ ); 143.75, 141.18, 141.03, 135.85, 131.83, 130.38, 128.82, 127.23, 127.06, 126.36, 123 .30, 122.93, 122.62, 122.12, 121.27, 120.71, 120.37, 117.72, 109.93, 109.85
Synthesis Example 2 Synthesis of 2-chloro-9- [4- (10H-phenoxazin-10-yl) phenyl] carbazole

  Synthetic Example 1 except that 9.2 g of 10- (4-bromophenyl) -10H-phenoxazine was used instead of 9.7 g of 10- (4-bromophenyl) -10H-phenothiazine and the reaction time was 12 h. The same operation was performed to isolate 9.1 g (19.8 mmol) of white powder of 2-chloro-9- [4- (10H-phenoxazin-10-yl) phenyl] carbazole (yield 80%, HPLC (Purity 99.2%).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.12 (d, 1H), 8.05 (d, 1H), 7.77 (d, 2H), 7.60 (d, 2H), 7.48 (s) , 3H), 7.35-7.24 (m, 2H), 6.73-6.67 (m, 6H), 6.08 (t, 2H)
¹³ C-NMR (CDCl ₃ ); 144.00, 141.07, 140.92, 138.29, 137.13, 134.12, 132.71, 131.88, 129.35, 126.42, 123 37, 123.00, 122.20, 121.72, 121.31, 120.83, 120.41, 115.66, 113.28, 109.89, 109.82
Synthesis Example 3 Synthesis of 2-chloro-9- [3- (10H-phenothiazin-10-yl) phenyl] carbazole

  Instead of 9.7 g of 10- (4-bromophenyl) -10H-phenothiazine, 9.7 g of 10- (3-bromophenyl) -10H-phenothiazine was used, and the obtained residue was subjected to silica gel column chromatography (toluene and hexane). The white powder of 2-chloro-9- [3- (10H-phenothiazin-10-yl) phenyl] carbazole was prepared in the same manner as in Synthesis Example 1 except that the mixture was purified with a mixed solvent (volume ratio 2/3)). 8.6 g (18.1 mmol) was isolated (yield 73%, HPLC purity 99.4%).

The compound was identified by FDMS.
FDMS (m / z); 475 (M +)
Synthesis Example 4 Synthesis of 2-chloro-9- [3- (10H-phenoxazin-10-yl) phenyl] carbazole

  Instead of 9.7 g of 10- (4-bromophenyl) -10H-phenothiazine, 9.2 g of 10- (3-bromophenyl) -10H-phenoxazine was used, and the obtained residue was subjected to silica gel column chromatography (toluene and Except for purification with a mixed solvent of hexane (volume ratio 2/3)), the same operation as in Synthesis Example 1 was carried out to obtain 2-chloro-9- [3- (10H-phenoxazin-10-yl) phenyl] carbazole. 8.2 g (17.9 mmol) of white powder was isolated (yield 72%, HPLC purity 99.3%).

The compound was identified by FDMS.
FDMS (m / z); 458 (M +)
Synthesis Example 5 Synthesis of 4-chloro-9- [4- (10H-phenothiazin-10-yl) phenyl] carbazole

  In a 200 mL three-necked flask under a nitrogen stream, 5.0 g (24.8 mmol) of 4-chloro-9H-carbazole, 9.7 g (27.3 mmol) of 10- (4-bromophenyl) -10H-phenothiazine, triphosphate 3 7.9 g (37.2 mmol) of potassium and 40 mL of o-xylene were added, and 56 mg (0.25 mmol) of palladium acetate and 176 mg (0.87 mmol) of tri-tert-butylphosphine were added to the resulting slurry reaction solution. The mixture was added and stirred at 140 ° C. for 12 hours. After cooling to room temperature, 25 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with a saturated aqueous sodium chloride solution, further dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio 2/3)), and white powder of 4-chloro-9- [4- (10H-phenothiazin-10-yl) phenyl] carbazole was obtained. 7.5 g (15.9 mmol) was isolated (yield 64%, HPLC purity 99.1%).

The compound was identified by FDMS.
FDMS (m / z); 475 (M +)
Synthesis Example 6 Synthesis of 4-chloro-9- [4- (10H-phenoxazin-10-yl) phenyl] carbazole

  The same operation as in Synthesis Example 5 was performed except that 9.2 g of 10- (4-bromophenyl) -10H-phenoxazine was used instead of 9.7 g of 10- (4-bromophenyl) -10H-phenothiazine, 7.7 g (16.9 mmol) of white powder of 4-chloro-9- [4- (10H-phenoxazin-10-yl) phenyl] carbazole was isolated (yield 68%, HPLC purity 99.2%) .

  The compound was identified by FDMS.

FDMS (m / z); 458 (M +)
Synthesis Example 7 Synthesis of 4-chloro-9- [3- (10H-phenoxazin-10-yl) phenyl] carbazole

  The same operation as in Synthesis Example 5 was performed except that 9.2 g of 10- (3-bromophenyl) -10H-phenoxazine was used instead of 9.7 g of 10- (4-bromophenyl) -10H-phenothiazine, 5.9 g (12.9 mmol) of white powder of 4-chloro-9- [3- (10H-phenoxazin-10-yl) phenyl] carbazole was isolated (yield 52%, HPLC purity 99.4%) .

The compound was identified by FDMS.
FDMS (m / z); 458 (M +)
Example 1 (Synthesis of Compound (A11))

  In a 50 mL three-necked flask under a nitrogen stream, 1.4 g (3.0 mmol) of 2-chloro-9- [4- (10H-phenothiazin-10-yl) phenyl] carbazole obtained in Synthesis Example 1 and N, N- Bisbiphenylamine (0.97 g, 3.0 mmol), sodium-tert-butoxide (0.40 g, 4.2 mmol), and o-xylene (15 mL) were added. To the resulting slurry reaction solution, 6.7 mg (0 0.03 mmol) and 21 mg (0.11 mmol) of tri-tert-butylphosphine were added and stirred at 140 ° C. for 6 hours. After cooling to room temperature, 15 mL of pure water was added and stirred. The product precipitated in the organic layer was collected by filtration and washed with water and methanol. The residue was recrystallized (toluene / butanol) to isolate 2.1 g (2.8 mmol) of a white powder of compound (A11) (yield 92%, HPLC purity 99.9%).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.08 (t, 2H), 7.67 (d, 2H), 7.57-7.37 (m, 15H), 7.31-7.14 (m, 10H), 7.07 (d, 2H), 6.87-6.79 (m, 4H), 6.40 (d, 2H)
¹³ C-NMR (CDCl ₃ ); 147.21, 146.09, 143.78, 141.73, 141.21, 140.53, 140.50, 136.41, 135.22, 130.47, 128 .75, 128.70, 127.74, 127.07, 127.00, 126.84, 126.63, 125.49, 123.79, 123.53, 123.10, 122.23, 121.20 , 120.51, 119.93, 119.85, 118.89, 117.42, 109.67, 106.39.
Example 2 (Synthesis of Compound (A14))

  Instead of 0.97 g of N, N-bisbiphenylamine, 0.86 g of 2-anilino-9,9-dimethylfluorene was used, and the residue was subjected to silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio 1/1). The procedure was the same as in Example 1 except that the white powder of A14 was isolated by 1.8 g (2.5 mmol) (yield 82%, HPLC purity 99.7%).

The compound was identified by FDMS.
FDMS (m / z); 723 (M +)
Example 3 (Synthesis of Compound (B3))

  Under a nitrogen stream, 1.4 g (3.0 mmol) of 2-chloro-9- [4- (10H-phenoxazin-10-yl) phenyl] carbazole obtained in Synthesis Example 2 was added to a 50 mL three-necked flask and N-phenyl. 0.81 g (3.0 mmol) of -9-phenanthrylamine, 0.40 g (4.2 mmol) of sodium-tert-butoxide, and 15 mL of o-xylene were added, and palladium acetate 6 was added to the resulting slurry reaction solution. 0.7 mg (0.03 mmol) and tri-tert-butylphosphine 21 mg (0.11 mmol) were added and stirred at 140 ° C. for 12 hours. After cooling to room temperature, 15 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with a saturated aqueous sodium chloride solution, further dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio 1/1)), and 1.3 g (1.9 mmol) of white powder of compound (B3) was isolated (yield 64%, HPLC purity 99.6%).

The compound was identified by FDMS.
FDMS (m / z); 691 (M +)
Example 4 (Synthesis of Compound (B7))

  The same procedure as in Example 3 was performed, except that 0.78 g of N- (4-tolyl) -4-biphenylamine was used instead of 0.81 g of N-phenyl-9-phenanthrylamine, and white color of B7 1.6 g (2.4 mmol) of powder was isolated (yield 79%, HPLC purity 99.8%).

The compound was identified by FDMS.
FDMS (m / z); 681 (M +)
Example 5 (Synthesis of Compound (B11))

  The same as Example 3 except that 0.97 g of N, N-bisbiphenylamine was used instead of 0.81 g of N-phenyl-9-phenanthrylamine, and the residue was purified by recrystallization (toluene / butanol). The operation was performed and 1.9 g (2.5 mmol) of a white powder of compound (B11) was isolated (yield 85%, HPLC purity 99.9%).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.08 (t, 2H), 7.72 (d, 2H), 7.57-7.48 (m, 11H), 7.44-7.37 (m, 5H), 7.33-7.15 (m, 9H), 6.62 (ddd, 6H), 5.98 (d, 2H)
¹³ C-NMR (CDCl ₃ ); 147.19, 146.13, 143.94, 141.59, 141.09, 140.51, 137.78, 137.53, 135.28, 134.09, 132 .44,129.12,128.75,127.75,126.85,126.63,125.54,123.79,123.60,123.33,121.56,121.24,120.63 119.96, 119.91, 118.97, 115.53, 113.22, 109.63, 106.37.
Example 6 (Synthesis of Compound (B12))

  Example 3 except that 0.96 g of N-phenyl-p-terphenylamine was used instead of 0.81 g of N-phenyl-9-phenanthrylamine, and the residue was purified by recrystallization (toluene / butanol). The same operation was performed, and 1.8 g (2.4 mmol) of a light yellow powder of B12 was isolated (yield 80%, HPLC purity 99.8%).

The compound was identified by FDMS.
FDMS (m / z); 743 (M +)
Example 7 (Synthesis of Compound (B16))

  The same operation as in Example 3 was carried out except that 0.89 g of N-phenyl-4- (1-naphthyl) phenylamine was used instead of 0.81 g of N-phenyl-9-phenanthrylamine. 1.3 g (1.9 mmol) of white powder was isolated (yield 62%, HPLC purity 99.7%).

The compound was identified by FDMS.
FDMS (m / z); 717 (M +)
Example 8 (Synthesis of Compound (B18))

  The same operation as in Example 3 was performed except that 1.00 g of N- [4- (carbazol-9-yl) phenyl] phenylamine was used instead of 0.81 g of N-phenyl-9-phenanthrylamine. , 1.8 g (2.4 mmol) of white powder of B18 was isolated (yield 80%, HPLC purity 99.8%).

The compound was identified by FDMS.
FDMS (m / z); 756 (M +)
Example 9 (Synthesis of Compound (A26))

  In a 50 mL three-necked flask under a nitrogen stream, 1.4 g (3.0 mmol) of 2-chloro-9- [3- (10H-phenothiazin-10-yl) phenyl] carbazole obtained in Synthesis Example 3 and N-phenyl- 4-biphenylamine 0.74 g (3.0 mmol), sodium-tert-butoxide 0.40 g (4.2 mmol), and o-xylene 15 mL were added, and 6.7 mg (palladium acetate) was added to the resulting slurry reaction solution. 0.03 mmol) and 21 mg (0.11 mmol) of tri-tert-butylphosphine were added and stirred at 140 ° C. for 6 hours. After cooling to room temperature, 15 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with a saturated aqueous sodium chloride solution, further dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio 1/1)), and 1.7 g (2.5 mmol) of white powder of compound (A26) was isolated (yield 84%, HPLC purity 99.9%).

The compound was identified by FDMS.
FDMS (m / z); 683 (M +)
Example 10 (Synthesis of Compound (B31))

  Instead of 1.4 g of 2-chloro-9- [4- (10H-phenothiazin-10-yl) phenyl] carbazole, 2-chloro-9- [3- (10H-phenoxazine-10] obtained in Synthesis Example 4 was used. -Yl) phenyl] carbazole The same operation as in Example 1 was performed except that 1.4 g was used, and 1.8 g (2.4 mmol) of a white powder of B31 was isolated (yield 80%, HPLC purity 99. 8%).

The compound was identified by FDMS.
FDMS (m / z); 743 (M +)
Example 11 (Synthesis of Compound (A81))

  In a 50 mL three-necked flask under a nitrogen stream, 1.4 g (3.0 mmol) of 4-chloro-9- [4- (10H-phenothiazin-10-yl) phenyl] carbazole obtained in Synthesis Example 5 and 0.51 g of diphenylamine were obtained. (3.0 mmol), 0.40 g (4.2 mmol) of sodium-tert-butoxide, and 15 mL of o-xylene were added, and 6.7 mg (0.03 mmol) of palladium acetate and triethyl chloride were added to the resulting slurry reaction solution. 21 mg (0.11 mmol) of (tert-butyl) phosphine was added and stirred at 140 ° C. for 10 hours. After cooling to room temperature, 15 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with a saturated aqueous sodium chloride solution, further dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio 1/1)), and 1.1 g (1.8 mmol) of white powder of compound (A81) was isolated (yield 60%, HPLC purity 99.6%).

The compound was identified by FDMS.
FDMS (m / z); 607 (M +)
Example 12 (Synthesis of Compound (A86))

The same operation as in Example 11 was carried out except that 0.74 g of N-phenyl-4-biphenylamine was used instead of 0.51 g of diphenylamine, and 1.5 g (2.1 mmol) of A86 white powder was isolated. (Yield 71%, HPLC purity 99.4%).
FDMS (m / z); 683 (M +)
Example 13 (Synthesis of Compound (B82))

  In a 50 mL three-necked flask under a nitrogen stream, 1.4 g (3.0 mmol) of 4-chloro-9- [4- (10H-phenoxazin-10-yl) phenyl] carbazole obtained in Synthesis Example 6 and N-phenyl -1-Naphtylamine 0.66 g (3.0 mmol), sodium-tert-butoxide 0.40 g (4.2 mmol), and o-xylene 15 mL were added, and 6.7 mg palladium acetate was added to the resulting slurry reaction solution. 0.03 mmol) and 21 mg (0.11 mmol) of tri-tert-butylphosphine were added and stirred at 140 ° C. for 15 hours. After cooling to room temperature, 15 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with a saturated aqueous sodium chloride solution, further dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio 1/1)), and 1.5 g (2.3 mmol) of white powder of compound (B82) was isolated (yield 76%, HPLC purity 99.6%).

The compound was identified by FDMS.
FDMS (m / z); 641 (M +)
Example 14 (Synthesis of Compound (B87))

  The same procedure as in Example 13 was performed, except that 0.78 g of N- (4-tolyl) -4-biphenylamine was used instead of 0.66 g of N-phenyl-1-naphthylamine, and 1 white powder of B87 was obtained. 0.3 g (2.0 mmol) was isolated (yield 66%, HPLC purity 99.5%).

The compound was identified by FDMS.
FDMS (m / z); 681 (M +)
Example 15 (Synthesis of Compound (B91))

  The same operation as in Example 13 was carried out except that 0.97 g of N, N-bisbiphenylamine was used instead of 0.66 g of N-phenyl-1-naphthylamine, and 1.6 g (2. 2 mmol) isolated (yield 74%, HPLC purity 99.7%).

The compound was identified by FDMS.
FDMS (m / z); 743 (M +)
Example 31 (Synthesis of Compound (B81))

  The same operation as in Example 13 was carried out except that 0.51 g of diphenylamine was used instead of 0.66 g of N-phenyl-1-naphthylamine, and 1.1 g (1.9 mmol) of white powder of B81 was isolated ( Yield 62%, HPLC purity 99.5%).

  The compound was identified by FDMS.

FDMS (m / z); 591 (M +)
Example 32 (Synthesis of Compound (B86))

  The same operation as in Example 13 was carried out except that 0.74 g of N-phenyl-4-biphenylamine was used instead of 0.66 g of N-phenyl-1-naphthylamine, and 1.3 g (1 0.9 mmol) isolated (yield 64%, HPLC purity 99.7%).

  The compound was identified by FDMS.

FDMS (m / z); 667 (M +)
Example 33 (Synthesis of Compound (B98))

  The same operation as in Example 13 was carried out except that 1.00 g of N- [4- (carbazol-9-yl) phenyl] phenylamine was used instead of 0.66 g of N-phenyl-1-naphthylamine. 1.3 g (1.7 mmol) of white powder was isolated (yield 58%, HPLC purity 99.7%).

  The compound was identified by FDMS.

FDMS (m / z); 756 (M +)
Example 34 (Synthesis of Compound (B106))

  Under a nitrogen stream, 1.4 g (3.0 mmol) of 4-chloro-9- [3- (10H-phenoxazin-10-yl) phenyl] carbazole obtained in Synthesis Example 7 was added to a 50 mL three-necked flask and N-phenyl. 0.74 g (3.0 mmol) of -4-biphenylamine, 0.40 g (4.2 mmol) of sodium-tert-butoxide, and 15 mL of o-xylene were added, and 6.7 mg of palladium acetate was added to the resulting slurry reaction solution. (0.03 mmol) and 21 mg (0.11 mmol) of tri-tert-butylphosphine were added and stirred at 140 ° C. for 15 hours. After cooling to room temperature, 15 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was washed with a saturated aqueous sodium chloride solution, further dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio 1/1)), and 1.4 g (2.1 mmol) of white powder of compound (B106) was isolated (yield 70%, HPLC purity 99.5%).

  The compound was identified by FDMS.

FDMS (m / z); 667 (M +)
Example 16 (Reduction characteristic evaluation of compound (A14))
Compound (A14) was dissolved in an anhydrous tetrahydrofuran solution having a concentration of n-tetrabutylammonium perchlorate of 0.1 mol / L at a concentration of 0.001 mol / L, and the reduction potential was measured by cyclic voltammetry. Glassy carbon was used for the working electrode, platinum wire was used for the counter electrode, and silver wire immersed in an acetonitrile solution of AgNO ₂ was used for the reference electrode. The compound (A14) is obtained by using the ferrocene oxidation-reduction potential as a reference at −3.30 V vs. Although it ran to Fc / Fc +, no reduction wave was observed. That is, it was confirmed that the compound (A14) having an electron donating phenothiazine ring is excellent in an electron blocking function.

Example 17 (Reduction characteristic evaluation of compound (B7))
Measurement was performed in the same manner as in Example 16 except that the compound (B7) was used instead of the compound (A14). Compound (B7) has a -3.30 V vs. ferro-reduction potential based on the ferrocene oxidation-reduction potential. Although it ran to Fc / Fc +, no reduction wave was observed. That is, it was confirmed that the compound (B7) having an electron-donating phenoxazine ring has an excellent electron blocking function.

Example 18 (Reduction characteristic evaluation of compound (B18))
Measurement was performed in the same manner as in Example 16 except that the compound (B18) was used instead of the compound (A14). Compound (B18) is obtained by using the redox potential of ferrocene as a reference at −3.30 V vs. Although it ran to Fc / Fc +, no reduction wave was observed. That is, it was confirmed that the compound (B18) having an electron donating phenoxazine ring is excellent in an electron blocking function.

Example 19 (Reduction characteristic evaluation of compound (A86))
Measurement was performed in the same manner as in Example 16 except that the compound (A86) was used instead of the compound (A14). Compound (A86) is obtained by using the redox potential of ferrocene as a reference at −3.30 V vs. Although it ran to Fc / Fc +, no reduction wave was observed. That is, it was confirmed that the compound (A86) having an electron donating phenothiazine ring is excellent in an electron blocking function.

Example 20 (Reduction characteristic evaluation of compound (B87))
Measurement was performed in the same manner as in Example 16 except that the compound (B87) was used instead of the compound (A14). Compound (B87) has a concentration of −3.30 V vs. ferro-reduction potential based on the oxidation-reduction potential of ferrocene. Although it ran to Fc / Fc +, no reduction wave was observed. That is, it was confirmed that the compound (B87) having an electron-donating phenoxazine ring has an excellent electron blocking function.

Example 35 (Reduction characteristic evaluation of compound (B81))
Measurement was performed in the same manner as in Example 16 except that the compound (B81) was used instead of the compound (A14). Compound (B81) is obtained by using the redox potential of ferrocene as a reference at −3.30 V vs. Although it ran to Fc / Fc +, no reduction wave was observed. That is, it was confirmed that the compound (B81) having an electron-donating phenoxazine ring has an excellent electron blocking function.

Example 36 (Reduction characteristic evaluation of compound (B86))
The measurement was performed in the same manner as in Example 16 except that the compound (B86) was used instead of the compound (A14). Compound (B81) is obtained by using the redox potential of ferrocene as a reference at −3.30 V vs. Although it ran to Fc / Fc +, no reduction wave was observed. That is, it was confirmed that the compound (B86) having an electron-donating phenoxazine ring has an excellent electron blocking function.

Example 37 (Reduction characteristic evaluation of compound (B98))
Measurement was performed in the same manner as in Example 16 except that the compound (B98) was used instead of the compound (A14). The compound (B98) has a -3.30 V vs. ferro-reduction potential based on the ferrocene redox potential. Although it ran to Fc / Fc +, no reduction wave was observed. That is, it was confirmed that the compound (B98) having an electron-donating phenoxazine ring has an excellent electron blocking function.

Example 38 (Reduction characteristic evaluation of compound (B106))
Measurement was performed in the same manner as in Example 16 except that the compound (B106) was used instead of the compound (A14). The compound (B106) has a -3.30V vs. ferro-reduction potential based on the oxidation-reduction potential of ferrocene. Although it ran to Fc / Fc +, no reduction wave was observed. That is, it was confirmed that the compound having an electron-donating phenoxazine ring (B106) was excellent in the electron blocking function.

Comparative Example 1
Measurement was performed in the same manner as in Example 16 except that the compound (a) shown below was used instead of the compound (A14). Compound (a) has a value of -2.75V vs. ferrocene based on the redox potential of ferrocene. A reduction wave was observed in Fc / Fc +. That is, it was confirmed that the compound (a) having an anthracene ring is inferior in the electron blocking function.

Example 21 (Element Evaluation of Compound (A11))
The glass substrate on which the ITO transparent electrode (anode) having a thickness of 200 nm was laminated was subjected to ultrasonic cleaning with acetone and pure water and boiling cleaning with isopropyl alcohol. Furthermore, ultraviolet / ozone cleaning was performed, and after evacuation with a vacuum pump until it was 1 × 10 ⁻⁴ Pa after installation in a vacuum deposition apparatus. First, copper phthalocyanine is deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / second to form a 10 nm hole injection layer. Subsequently, the compound (A11) is deposited at a deposition rate of 0.3 nm / second to 30 nm to form holes. A transport layer was used. Subsequently, tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ) as a phosphorescent dopant material and 4,4′-bis (N-carbazolyl) biphenyl (CBP) as a host material have a weight ratio of 1:11. Co-deposited at a deposition rate of 0.25 nm / second to obtain a 30 nm emission layer. Next, BAlq (bis (2-methyl-8-quinolinolato) (p-phenylphenolate) aluminum) was deposited at a deposition rate of 0.3 nm / second to form a 5 nm exciton block layer, and then Alq ₃ (Tris (8-quinolinolato) aluminum) was deposited at 0.3 nm / second to form a 45 nm electron transport layer. Subsequently, lithium fluoride was deposited as an electron injection layer by 1 nm at a deposition rate of 0.01 nm / second, and aluminum was deposited by 100 nm at a deposition rate of 0.25 nm / second to form a cathode. In a nitrogen atmosphere, a sealing glass plate was bonded with a UV curable resin to obtain an organic EL element for evaluation. A current of 20 mA / cm ² was applied to the device thus fabricated, and driving voltage and current efficiency were measured. The luminance half time of the device was evaluated by applying a current of 6.25 mA / cm ² . The results are shown in Table 1. In addition, about element lifetime, it represented with the relative value which set the element lifetime of the comparative example 1 mentioned later to 100.

Example 22
An organic EL device was produced in the same manner as in Example 21 except that the compound (A14) was used instead of the compound (A11). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 23
An organic EL device was produced in the same manner as in Example 21 except that the compound (A26) was used instead of the compound (A11). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 24
An organic EL device was produced in the same manner as in Example 21 except that the compound (B7) was used instead of the compound (A11). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 25
An organic EL device was produced in the same manner as in Example 21 except that the compound (B11) was used instead of the compound (A11). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 26
An organic EL device was produced in the same manner as in Example 21 except that the compound (B18) was used instead of the compound (A11). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 27
An organic EL device was produced in the same manner as in Example 21 except that the compound (B31) was used instead of the compound (A11). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 28
An organic EL device was produced in the same manner as in Example 21 except that the compound (A86) was used instead of the compound (A11). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 29
An organic EL device was produced in the same manner as in Example 21 except that the compound (B87) was used instead of the compound (A11). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 30
An organic EL device was produced in the same manner as in Example 21 except that the compound (B91) was used instead of the compound (A11). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 39
An organic EL device was produced in the same manner as in Example 21 except that the compound (B81) was used instead of the compound (A11). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 40
An organic EL device was produced in the same manner as in Example 21 except that the compound (B86) was used instead of the compound (A11). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 41
An organic EL device was produced in the same manner as in Example 21 except that the compound (B98) was used instead of the compound (A11). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Example 42
An organic EL device was produced in the same manner as in Example 21 except that the compound (B106) was used instead of the compound (A11). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Comparative Example 2 (NPD element evaluation)
An organic EL device was produced in the same manner as in Example 21 except that NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl) was used instead of the compound (A11). . Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

Comparative Example 3 (Device evaluation of compound (a))
An organic EL device was produced in the same manner as in Example 21 except that the compound (a) described above was used instead of the compound (A11). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied, and the luminance half time when a current of 6.25 mA / cm ² was applied.

  The carbazole compound of the present invention can be used as a hole injection material, a hole transport material, or a host material for a light emitting layer of an organic EL device, and has a device efficiency and a lifetime that are higher than those of organic EL devices using conventionally known materials. Excellent. Furthermore, not only as a hole injection material, a hole transport material or a light emitting material of an organic EL element or an electrophotographic photosensitive member, but also in a field to an organic photoconductive material such as a photoelectric conversion element, a solar cell, or an image sensor. Applicable.

Claims (7)

A carbazole compound represented by the general formula (1).

(In the formula, X represents a 1,4-phenylene group or a 1,3-phenylene group. Y represents a sulfur or oxygen atom. R ^{1 to} R ⁸ each independently represents a hydrogen atom, a methyl group, or A group represented by the following general formula (2) is represented, and at least one of R ^{1 to} R ⁸ is a group represented by the following general formula (2).

(In the formula, Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 18 carbon atoms or a 4- (carbazol-9-yl) phenyl group, and these groups are each independently And may have a methyl group or a methoxy group.) R ¹ , R ³ , R ⁶ and R ⁸ are each independently a hydrogen atom or a methyl group, and R ² , R ⁴ , R ⁵ and R ⁷ are each independently a hydrogen atom, a methyl group, Or a group represented by the general formula (2), wherein at least one of R ² , R ⁴ , R ⁵ and R ⁷ is a group represented by the general formula (2). The carbazole compound described in 1. Ar ¹ and Ar ² are each independently a phenyl group, a tolyl group, a biphenylyl group, a terphenyl group, a 9,9-dimethyl-9H-fluorenyl group, or a 4- (carbazol-9-yl) phenyl group. The carbazole compound according to claim 1 or 2, wherein   The carbazole compound according to any one of claims 1 to 3, wherein X is a 1,4-phenylene group.   The carbazole compound according to claim 1, wherein Y is an oxygen atom. Structural formulas A6, A7, A11, A14, A18, A26, A31, A38, A86, A87, A91, A107, B6, B7, B10, B11, B12, B14, B18, B26, B31, B38, B81, B86 The carbazole compound according to claim 1, represented by any one of: B87, B91, B98, and B106.

  A light-emitting host material, or a hole transport material and a hole injection material, comprising the carbazole compound according to claim 1.